Patent GB-541649-A (GB)
Title: Improvements relating to the use of aromatic compounds in photography
IPC: G03C5/30
Filed: 1940-03-01
Abstract: 541,649. Aromatic amines. KODAK, Ltd. (Eastman Kodak Co.). March 1, 1940, No. 3845. [Class 2 (iii)] [Also in Group XX] A photographic developing solution contains as the developing agent a compound of the formulain which A is an OH or NH  2  group and is in an ortho or para position to the substituted amino group ; R is hydrogen, or a substituted or unsubstituted alkyl, aryl, heterocyclic, cycloaliphatic, or unsaturated aliphatic group, or a grouping of the type -YR<SP>1</SP>: Y is an organic grouping : and R<SP>1</SP> is an acetal group of the type where X and X<SP>1</SP> are substituted or unsubstituted alkyl, aryl, heterocyclic, cycloaliphatic, or unsaturated aliphatic groups, or of the type where any of the hydrogen atoms can be replaced by groups of the type X and X<SP>1</SP> above. The benzene ring may form part of a naphthalene or other poly-nuclear system, and the benzene ring or polynuclear system may be further substituted by one or more halogen atoms or alkyl, alkoxy, hydroxy, or amino groups. A may be a substituted amino group, and Y may be a group of the type (CH 2 ) n , where n is 1, 2 or other integer, and any of the hydrogen atoms can be replaced by substituted or unsubstituted alkyl, aryl, heterocyclic, cycloaliphatic, or unsaturated aliphatic groups. General methods given for the preparation of the amino compounds of the above general formula include the reduction of the corresponding nitro; azo, or nitroso compounds. The corresponding nitro compounds may be prepared either (a) by re-action of a compound NO 2 - C 6 H 4 -NHR with a compound Halogen-Y-R<SP>1</SP> or (b) by re-action of a compound NO 2 .C 6 H 4 . Halogen with a compound HNR, Y-R<SP>1</SP> or (c) by re-action of a compound NO 2 .C 6 H 4 NHY.R<SP>1</SP> with a re-agent such as RCl, or an alkyl or alkylene oxide. P - (# - # - dimethoxyethylamino) - nitroben ene is prepared by the re-action of pnitrochlorobenzene and the acetal from methyl alcohol and aminoacetaldehyde in the presence of sodium bicarbonate. P - (#: # - dimethoxyethylamino) - aniline is prepared by the reduction of the corresponding nitro compound with hydrogen in the presence of Raney nickel catalyst. The corresponding di-(#:#-dimethoxyethyl) derivative is similarly prepared. The reduction may be effected with sodium sulphide, or by hydrogenating in the presence of nickel, butylamine being present to prevent splitting of the acetal group. P - (# : # - diethoxyethyl N - methylamino) - phenol is prepared by the re-action of p-hydroxy-. N-methyl aniline and bromoacetal in the presence of sodium bicarbonate. Compounds (4), (5), (6), and (8) above are similarly prepared. # - bromoethyl - αα - di - (ethoxyethylether) is prepared by brominating ethyl-αα-di-(ethoxyethylether) at 60-90‹ C. under the action of ultra-violet light. Bromo-n-propyl-αα-di- (methylether) is similarly prepared. Ethylene glycol #-(4-hydroxy-2-aminophenylamino)-ethylideneether is prepared by reducing the condensation product from 2-nitro-4-hydroxychloro-benzene and ethylene glycol #-aminoethylidene ether by hydrogenation in the presence of nickel and butylamine. γ - hydroxy - n - propylene α .: # - glycol p - hydroxyphenyl N - he adecyl - amino) - ethylidene ether is prepared by re-acting phydroxyaniline with cetyl bromide, and reacting the product with α-hydroxy-n-propylene- α:#-glycol # bromo-ethylidene ether. 4 - (# : # - di - (# - methoxyethoxy) - ethyl - N - p - hydroxyphenylamino) - 3 - chlorophenol is prepared by condensing p-nitrochloro-benzene with 2-chloro-4-hvdroxyaniline, converting the nitro group to hydroxy by reducing, diazotizing, and boiling in water, and condensing with #-bromo-αα-(methoxyethoxy)-ethane. Compound (11) is similarly prepared. Ethylene glycol o-hydroxyphenyl-N-#-hydroxyethyl-aminomethylene ether is prepared by diazotization of the corresponding amino compound and allowing the diazo compound produced to de-compose in neutral solution. The amino compound can be prepared either by heating- o-nitrochlorobenzene first with ethanol-amine and then with #-bromo-n-propylene-α:#-methylene ether or by heating onitrochlorobenzene first with #-amino-n-propylene-α-#-methylene ether and then with ethylene oxide, the nitro group being subsequently reduced to amino. Specifications 2562/13, [Class 98 (ii)], 390,093; 397,159, 427,520, [both in Group XX], 447,748; 458,664, 458,665, [both in Group XX], 474,353, 478,933, 478,934, 478,942, 478,983, 478,984, 478,985 ; 478,986, [Group XX], 478,989, 478,990, 478,991 ; 493,952, 496,195, 496,196, 496,245, 502,960, 503,752, 509,707, [all in Group XX], and 537,466, are referred to.